CN104342633B - Volatile dihydropyrazinyl and dihydropyrazine metal complexes - Google Patents

Volatile dihydropyrazinyl and dihydropyrazine metal complexes Download PDF

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CN104342633B
CN104342633B CN201410363662.5A CN201410363662A CN104342633B CN 104342633 B CN104342633 B CN 104342633B CN 201410363662 A CN201410363662 A CN 201410363662A CN 104342633 B CN104342633 B CN 104342633B
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metal
alkyl
dihydro
independently selected
base
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CN104342633A (en
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S·V·伊万诺夫
雷新建
J·A·T·诺曼
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Versum Materials US LLC
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    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
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    • C07D241/12—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD

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Abstract

Described herein are compositions comprising dihydropyrazinyl anions that can coordinate as 6-electron ligands to a wide range of different metals to produce volatile metal complexes for ALD and CVD deposition. Also described herein are non-deprotonated dihydropyrazines which can coordinate to a metal as stabilized neutral ligands. In one embodiment, the composition is used to deliver a metal dihydropyrazinyl complex precursor by direct liquid injection into an ALD or CVD chamber for deposition of metal-containing thin films, such as ruthenium or cobalt metal films.

Description

Volatile dihydro pyrazine base and dihydro pyrazine metal complex
Background of invention
This document describes dihydro pyrazine part, it can be used for for example synthesizing metal complex, the metal complex example Such as it is not limited to be used as the ruthenium and the complex of cobalt of ALD or cvd precursor.There is also described herein the cooperation comprising dihydro pyrazine part Thing and the method for manufacturing or using the complex.
The source that electron trade persistently seeks precursor of the volatility containing metal is used for gas-phase deposition, including chemical gaseous phase Deposition (CVD) and ald (ALD) use these to contain precursors of metal in substrate (such as silicon, metal nitride, metal Oxide and other metal-containing layers) on make conformality and contain metal film.In these techniques, the steam of volatile metal complex Be introduced into process chamber, and contact silicon wafer surface in the process chamber, on the silicon wafer surface occur depositing pure gold category or The chemical reaction of metal compound film.If the precursor wafer surface occur thermal response or with simultaneously be added to process chamber In reagent reacting, then CVD occur, and with steady state deposition occur film grow.CVD can with continuous or pulse mode application, with Reach desired film thickness.In ALD, the precursor chemical is adsorbed onto on chip as self-saturation individual layer, excessive unreacted Precursor inert gas such as argon gas is purged, and being subsequently adding excess reagent should be to form gold with the single-layer back of the precursor of chemisorbed Category or metallic compound.Then excessive reagent is fallen with inert gas purge.Then this can be circulated repeatedly several times so that gold The expectation thickness of atomic accuracy are arrived in category or metallic compound accumulation, because the chemisorbed of precursor and reagent is self-limited type (self-limiting).ALD provides ultra-thin and the continuously deposition containing metal film, its precise control film thickness, film thickness Excellent homogeneity and surpassingly conformal film growth, with the etching of uniform coating depth and the structure of high complexity, such as interconnection is logical Hole and groove.The suitable metal precursor of ALD includes thermally-stabilised right to exclude any thermal decomposition occurred in the chemisorbed stage The reagent of addition have it is chemically reactive those.Additionally, it is important that metal precursor be monomer with maximum volatility and Clean evaporation, leaves behind micro non-volatilizable residue.It is also expected to precursor has high-dissolvability in hydrocarbon solvent, to be formed Can be used for direct liquid injection (DLI) to deliver the solution of precursor vapor to CVD or ALD reactors.Hydrocarbon solvent such as cyclooctane It is particularly attractive with mesitylene, because they are relatively high boiling liquid and can easily dry to low moisture water It is flat.
Ruthenium and cobalt be for being manufactured in semiconductor devices in the particularly attractive metal of CVD and ALD techniques.Ruthenium it is super The electrode or offer that the deposition of film can be used for making in DRAM capacitor battery are grown in copper diffusion barrier material as nitrogenized Copper adhesion on titanium or tantalum nitride promotes film.Ultra-thin continuous ruthenium film be also used as copper metal can Direct Electroplating thereon Crystal seed layer.Similarly, thin cobalt layers are also used as titanium nitride or the adhesion of tantalum nitride promotes film.As an alternative, cobalt can To deposit on copper interconnecting line as " epiphragma (capping film) ".When titanium nitride, tantalum nitride or other can be to element When oxygen deposits any metal on the substrate with reactivity, it is particularly desirable to which the complex of ruthenium and cobalt does not contain elemental oxygen, because this To tend to form the metal oxide that can cause electric fault in the device of manufacture.
The ruthenium precursor of many is reported in Chemistry Literature, but the common technique faced when they are used for into ALD is chosen War is, their induction times long when continuous metal film is formed and needs to use oxygen or ozone as reagent.Induction time long It is that, due to low metal atomic deposition (nucleation) density in earliest ALD cycle, it is slowly increased with further circulation, Because atomic nucleus tends to act as the site of further metal deposit.After foring enough nucleation densities, ALD film is formd thick Linear relationship between degree and the period of ALD.In that way it is possible to need up to 500 initial ALD cycles to form the ruthenium of stabilization Layer-growth rate (S.Yim etc., Journal of Applied Physics, 103,113509,2008).Nucleation density can lead to Application plasma is crossed during ALD techniques to improve, but compared with hot ALD, the highly directional vector quantization tendency of plasma In the uniformity for reducing deposition, especially can be with the upright side walls of the deep etching structure of " avoiding " plasma.It is another The use of aspect, oxygen and tetrabase can exist in the ability of their oxidative damage barrier films such as titanium nitride and tantalum nitride asks Topic, and also result in roughening and the etching of ruthenium metal.At this point, strong need exploitation heavy by chemical reduction process Product ruthenium metal and therefore avoid the ruthenium precursor of oxidative damage.Suitable agent for reducing includes, but are not limited to：Hydrogen, ammonia, amine Class, hydrazine, silanes, aluminium alkanes and boranes.The desired technique of topnotch will include being free of the ruthenium precursor of elemental oxygen and go back The combination of former agent.Similarly, it is desired to the reproducibility growth of the cobalt metal film for being formed by oxygen-free cobalt precursors under the reducing conditions. Therefore, needing in a word can be by also original deposited metal ruthenium and the oxygen-free ruthenium and cobalt precursors of cobalt.
Other metal precursors described in the prior include, but not limited to it is following in one or more：Cyclopentadiene Base (Cp), pyrroles, imidazoles, diene, CO, alkyl-substituted phenyl, amidine class (amidinates), guanidine (guanidinates) or Its combination.However, ligands and complexes described herein from it is of the prior art those are different because they be based on it is non-aromatic Dihydro pyrazine part, it is allowed by the high response of ALD and CVD growth metal film and not oxygen-containing.
Summary of the invention
This document describes the complex containing metallic hydrogen pyrazine with formula 3A to 3E described herein.In some embodiment party In formula, metal M is selected from Ru or Co.In some embodiments, the complex can be used for the direct of such as ALD and CVD techniques Liquid injection (DLI).These complexs can further include one or more solvent, such as hydrocarbon or other solvents, and quilt Pack or be contained in rustless steel container.
Term " metal dihydride pyrazinyl complex " is generally used for referring to the complex of the anion of base containing dihydro pyrazine, and term " metal dihydride pyrazine complex " is generally used for referring to the complex containing neutral dihydro pyrazine part.However, appointing in these terms One generally may serve to refer to complex of the invention herein.
There is also described herein N- alkyl dihydro pyrazine and N- trialkylsilkl dihydro pyrazines.
There is also described herein ALD and CVD deposition, it uses the cooperation containing metallic hydrogen pyrazine in depositing operation Thing, the complex more specifically containing ruthenium and cobalt, and selected from hydrogen, ammonia, hydrazine, silanes, boranes reducing agent.
There is also described herein ALD and CVD deposition, it uses the complex containing metallic hydrogen pyrazine, more specifically contains There are the complex of ruthenium and cobalt, and oxidant such as ozone or oxygen.
This document describes the composition comprising metal dihydride pyrazinyl complex, it can be used for DLI and delivers these precursors use In gas-phase deposition, such as ald (ALD) and chemical vapor deposition (CVD) growth containing metal film.In order that this A little precursors are delivered via DLI, and these precursors easily should also be dissolved with sufficiently high concentration, to form suitable DLI deliverings Composition.The composition of metal dihydride pyrazinyl complex described herein preferably shows volatility and heat under gasification condition Both stability.In addition, they are used as before in metal film growth and any other application for needing volatile metal precursors source Body is preferably highly effective.
In a still further aspect, there is provided the method that metal oxide film is formed on substrate, wherein the film has There is thickness, methods described includes：
A. the metal dihydride pyrazinyl selected from formula 3A, 3B, the complex of 3C, 3D, 3E, 3F, 3G and 3H or its combination is introduced Complex；
B. the metal dihydride pyrazinyl coordination chemistry is adsorbed on the substrate；
C. the metal dihydride pyrazinyl complex is purged using purge gas；
D. by oxygen source provide to heating substrate on the metal dihydride pyrazinyl complex with the metal for being adsorbed Dihydro pyrazine basigamy compound reacts；With
E. any unreacted oxygen source, wherein repeat step a to d are optionally purged until obtaining desired thickness Degree.
Other side of the invention includes：
#1. compositions, it includes one or more compound with following formula 3A, 3B and 3C：
Wherein R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or cyclic alkyl；R5It is former independently selected from H Son and C1-C6Straight chain, side chain or cyclic alkyl；(L) it is selected from cyclopentadienyl group, five alkyl cyclopentadienyls, pentamethyl ring penta 2 Alkenyl, dimethylcyclo-pentadienyl, front three cyclopentadienyl group, methyl cyclopentadienyl, ethyicydopentadi etanyf group, imidazole radicals, The anion of trialkylimidazolium base, pyrrole radicals and alkyl pyrrole radicals；M is divalent metal；X=1 or 2；X+y=2；X is independently selected From H atom, C1-C6Straight chain, side chain or cyclic alkyl and SiR6And wherein R6Independently selected from C1-C3Straight or branched alkyl.
#2. compositions, comprising the compound with formula 3D, it is included：
Wherein R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or cyclic alkyl；R5It is former independently selected from H Son and C1-C6Straight chain, side chain or cyclic alkyl；(L) it is selected from cyclopentadienyl group, five alkyl cyclopentadienyls, pentamethyl ring penta 2 Alkenyl, dimethylcyclo-pentadienyl, front three cyclopentadienyl group, methyl cyclopentadienyl, ethyicydopentadi etanyf group, imidazole radicals, The anion of trialkylimidazolium base, pyrrole radicals and alkyl pyrrole radicals；M is monovalent metal；X=1；Y=1 or 2；Z is independently selected from H Atom, C1-C6Straight chain, side chain or cyclic alkyl and SiR6, wherein R6Independently selected from C1-C6Straight or branched alkyl.
#3. compositions, comprising the compound with following formula 3E, it is included：
Wherein R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or cyclic alkyl；R5It is former independently selected from H Son and C1-C6Straight chain, side chain or cyclic alkyl；(Q) benzene and alkylated benzenes are selected from；M is metal；X is 1 or 2；Y=1；Z is independently Selected from H atom and C1-C6Straight or branched alkyl or ring-type C3-C6Alkyl and SiR6, wherein R6It is C1-C3Straight or branched Alkyl.
The method that #4. forms metal oxide film on substrate, wherein the film has thickness, methods described includes：
A. it is at least one in being introduced into comprising formula 3A, 3B of being selected from, the compound of 3C, 3D, 3E, 3F, 3G, 3H or its combination Metal dihydride pyrazinyl complex；
B. the metal dihydride pyrazinyl coordination chemistry is adsorbed on the substrate；
C. metal dihydride pyrazinyl complex is purged using purge gas；
D. by oxygen source provide the metal dihydride pyrazinyl complex to the substrate of heating with containing having adsorbed The composition reaction of metal dihydride pyrazinyl complex；With
E. any unreacted oxygen source is optionally purged.
, according to the method for #4, wherein repeat step a to d and optional step e is up to the film thickness described in formation for #5..
According to the method for #4, wherein methods described is atom layer deposition process to #6..
#7. is according to the method for #4, wherein the metal dihydride pyrazinyl complex is comprising selected from least one in following： (pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium, (pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) cobalt, (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) (benzene) ruthenium, and combinations thereof.
The method that #8. forms metal film on substrate, wherein the film has thickness, methods described includes：
A. it is at least one in being introduced into comprising formula 3A, 3B of being selected from, the compound of 3C, 3D, 3E, 3F, 3G, 3H or its combination Metal dihydride pyrazinyl complex；
B. the metal dihydride pyrazinyl coordination chemistry is adsorbed on the substrate；
C. metal dihydride pyrazinyl complex is purged using purge gas；
D. by reducing agent provide to heating substrate on the metal dihydride pyrazinyl complex with the gold for being adsorbed The compound reaction of category dihydro pyrazine basigamy；With
E. any unreacted reducing agent is optionally purged.
, according to the method for #8, wherein repeat step a to d and optional step e is up to the film thickness described in formation for #9..
According to the method for #8, wherein methods described is atom layer deposition process to #10..
#11. is according to the method for #8, wherein the metal dihydride pyrazinyl complex is comprising selected from least one in following Compound：(pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium, (pentamethyl ring penta Dialkylene) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) cobalt, (2,2- dihydro -3,3- dimethyl -5,6- diethyl Pyrazine) (benzene) ruthenium and combinations thereof.
#12. is according to the method for #8, wherein the reducing agent is selected from hydrogen, hydrogen plasma, ammonia, ammonia plasma treatment, hydrogen/nitrogen Plasma, alkyl silane and its mixture.
#13. compositions, comprising one or more compound with following formula 3F, 3G and 3H：
Wherein R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or cyclic alkyl；R5It is former independently selected from H Son and C1-C6Straight chain, side chain or cyclic alkyl；(Q) it is neutral ligand；M is monovalent metal；Y=1；X independently selected from H atom, C1-C6Straight chain, side chain or cyclic alkyl and SiR6And wherein R6Independently selected from C1-C3Straight or branched alkyl.
On the feature of one aspect of the invention description can be used for it is related to the present invention it is any other in terms of.
Brief Description Of Drawings
Fig. 1 shows (pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium Structure.
Fig. 2 provides (pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium (Cp*RuDMDEP) thermogravimetric analysis (TGA)/differential scanning calorimetric analysis (DSC) result.
Fig. 3 shows the knot of (pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) cobalt Structure.
Fig. 4 provides (pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) cobalt TGA/DSC results.
Fig. 5 shows the structure of (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) (tetrahydrofuran) potassium.
Fig. 6 is to use Cp*RuDMDEP/ oxygen at 300 DEG C in TiO2On ALD ruthenium films x-ray photoelectron power spectrum [XPS]。
Detailed description of the invention
This document describes the composition comprising dihydro pyrazine base anion, the dihydro pyrazine base anion can be as 6 Electron donor ligand is coordinated with different metal in extensive range, to produce the volatility complex for ALD and CVD.In some implementations In mode, the dihydro pyrazine base anion of height space substitution is suitable for inclusion in the complex of alkaline-earth metal.In other embodiment party In formula, the dihydro pyrazine base of less space substitution is applied to the further complex comprising transition metal and lanthanide series metal.More In further embodiment, the dihydro pyrazine of neutral non-deprotonation can be used as such as 4 e-donor ligands.For latter reality Mode is applied, the ruthenium complex of zeroth order can be made 18 electricity by dihydro pyrazine (4 electronics), ruthenium (0) (8 electronics) and toluene (6 electronics) Sub- complex.The advantage of dihydro pyrazine part described herein be it can due to be bonded to the hydrogen of ring nitrogen and to water or hydroxyl (OH) there is reactivity, it causes hydrolysis/open loop and follow-up metal or metal oxide film to deposit.It is not bound by theory, this Inventor thinks that the reactivity in this should be than the similar complex of the cyclohexadiene ligand with not facile hydrolysis more Greatly.In further embodiment, the dihydro pyrazine of neutral and non-deprotonation can with other parts be used together with The ligand-complexes of mixing are formed, described other parts such as cyclopentadiene (Cp), pyrroles, imidazoles, amidine, guanidine, diimine, ketone is sub- Amine, diketone etc..The composition comprising dihydro pyrazine part disclosed herein or complex for being generated are so that they are both to deposition Technique (more specifically, atom layer deposition process) has volatility, and thermally-stabilised under gasification condition.In addition to that mentioned above, institute State compound or complex and the composition comprising the compound or complex can be used as the precursor of metal film growth, it is described Metal films such as, but not limited to, ruthenium or cobalt metal film, and need any other application in volatile metal precursors source.
Metal dihydride pyrazinyl complex described herein contains selected from the 2nd race to the 16th race or the 4th race to the 16th race One or more metal.In some implementation methods of formula described herein, M is the metal selected from the 4th race to the 16th race, bag Include but be not limited to, Fe, Co, Ni, Cr, Mn, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, In, Ge, Sn, Sb, Te, Bi, Ti, Zr, Hf, V、Nb、Ta、Cr、Mo、W、Al、In、Sn、Sb、Bi；La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and its Combination.In a special implementation method, M is Ru.In another special implementation method, M is Co.
This document describes the synthesis of metal dihydride pyrazinyl complex, the complex is such as, but not limited to, based on dihydro The oxygen-free ruthenium and cobalt precursors of pyrazine ligand.These noval chemical compounds are monomers, neatly volatile and be highly soluble in In hydrocarbon solvent.The dihydro pyrazine part can be using in the form of its deprotonation as dihydro pyrazine base anion, as dihydro Pyrazinyl free radical anion is incorporated in these novel complexes as neutral (non-deprotonation) part.These are different Part configuration is shown in formula 1.
In addition, N- alkyl dihydro pyrazine or N- trialkylsilkls dihydro pyrazine can also be used as neutral molecule or conducts N- alkyl dihydro pyrazine bases or N- trialkylsilkls dihydro pyrazine base free radical anion and be incorporated in these novel complexes. These part configurations are shown in formula 2 for N- trialkylsilkl dihydro pyrazines.
Metal dihydride pyrazinyl complex can be formed, it contains and has more than a dihydro pyrazine base anion, or more than one Individual dihydro pyrazine base free radical anion, or more than a N- alkyl dihydro pyrazine base free radical anion or more than a N- tri- AIkylsilyl groups dihydro pyrazine base free radical anion.
In another embodiment, complex can be formed, it comprises only a dihydro pyrazine base anion, or containing only There is a dihydro pyrazine base free radical anion, or comprise only a N- alkyl dihydro pyrazine base free radical anion or comprise only One trialkylsilkl dihydro pyrazine base free radical anion, and other different anions are combined, such as pentamethyl ring penta Dialkylene.These complexs are shown in formula 3A, 3B and 3C, wherein R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain Or cyclic alkyl；R5Independently selected from H atom or straight chain, side chain or ring-type C1-C6Alkyl；R6Independently selected from C1-C3Straight chain or Branched alkyl；(L) it is selected from cyclopentadienyl group, pentamethylcyclopentadiene base, dimethylcyclo-pentadienyl, front three butylcyclopentadiene Base, methyl cyclopentadienyl, ethyicydopentadi etanyf group, imidazole radicals, trialkylimidazolium base, pyrrole radicals and alkyl pyrrole radicals it is cloudy from Son；M is divalent metal；X=1 or 2；X+y=2；X in formula 3C is independently selected from H atom, C1-C6Straight chain, side chain or ring-type alkane Base and SiR6And wherein R6Independently selected from C1-C3Straight or branched alkyl.
Preferably, R1And/or R2It is ethyl.Preferably, R3And/or R4It is methyl.Preferably, R5It is hydrogen.
In the further implementation method of formula 3D to 3H, can have the M or monovalent metal of "+1 " oxidation state.At this In a little implementation methods, R1、R2、R3、R4、R5、R6It is as described herein, and (Q) is neutral ligand, such as but not limited to, benzene or alkyl Change benzene.But when x is 1, y is changed into 0 (for example, L does not exist)；New variable " z " is 1.It is general in the case where M is monovalence Example will be following：(anion)xM+n(L)y(Q)z..The more specifically example of these compounds is represented by following formula 3F, 3G and 3H.
The complex containing neutral (non-deprotonation) dihydro pyrazine shown in formula 3D, wherein R can also be formed1、R2、 R3And R4It is each independently selected from C1-C6Straight chain, side chain or cyclic alkyl；R5Independently selected from H atom or C1-C6Straight chain, side chain Or cyclic alkyl；(L) it is selected from cyclopentadienyl group, five alkyl cyclopentadienyls, pentamethylcyclopentadiene base, diformazan basic ring penta 2 Alkenyl, front three cyclopentadienyl group, methyl cyclopentadienyl, ethyicydopentadi etanyf group, imidazole radicals, trialkylimidazolium base, pyrroles The anion of base and alkyl pyrrole radicals；M is monovalent metal；X=1 or 2；Y=1；Z is independently selected from H atom, C1-C6Straight chain, branch Chain or cyclic alkyl and SiR6, wherein R6Independently selected from straight chain, side chain or ring-type C1-C3Alkyl.
The complex containing neutral (non-deprotonation) dihydro pyrazine shown in formula 3E, wherein R can also be formed1、R2、 R3And R4It is independently of one another C1-C6Straight chain, side chain or cyclic alkyl；R5It is H atom or C1-C6Straight chain, side chain or cyclic alkyl； (Q) it is benzene or alkylated benzenes；M is the metal that oxidation state is 0；X is 1 or 2；Y=1, Z are independently selected from H atom or C1-C6Straight chain, Side chain or cyclic alkyl or SiR6, wherein R6It is straight chain, side chain or ring-type C1-C3Alkyl.
Preferably, Z is hydrogen.
In above-mentioned formula 3A, 3B, 3C and 3D, (L) can also be different from (dihydro pyrazine)xDihydro pyrazine anion, Dihydro pyrazine free radical anion, N- alkyl dihydro pyrazines free radical anion, N- trialkylsilkl dihydro pyrazine freedom Base anion.
The dihydro pyrazine base anion of the disclosure is shown as being coordinated with η -5 modes and ruthenium, (the pentamethyl as shown in figure (1) Cyclopentadienyl group) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium, the C1 of wherein Ru1 and DMDEP parts, N1, C6, C3 and N2 bonding.So, DMDEP anion serve as 6 electron donors, wherein formal 2 electronics are by anion negative electricity Lotus provides, followed by each of from part two double bonds provides 2 extra electronics.So, dihydro pyrazine Ji Yin from Son may assist in the complex that 18 electron coordinates layer is provided around transition metal to provide stabilization.Therefore, in (pentamethyl ring penta Dialkylene) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium example in, six (d) electronics are by Ru+2There is provided, Six come from pentamethylcyclopentadiene base anion from dihydro pyrazine base anion and six electronics, to produce 18 electricity altogether Son.Neutral (non-deprotonation) dihydro pyrazine part, N- alkyl dihydro pyrazine or trialkylsilkl dihydro pyrazine can be with As four electron donors be similar to lateral η -4 modes and metal-complexing, two electronics by part two double bonds each There is provided.Referring now to Fig. 3 or (pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) cobalt, Structure, eight (d) electronics are by Co+1There is provided, six electronics are provided by pentamethylcyclopentadiene base anion, four electronics come from two Hydrogen pyrazine ligand, to produce 18 electronics altogether.N- alkyl dihydro pyrazine and N- trialkylsilkls dihydro pyrazine can lead to An electron reduction is crossed, to form N- alkyl dihydro pyrazine bases and N- trialkylsilkl dihydro pyrazines Ji Ziyoujiyin respectively Ion, makes their negative electrical charge across four atom delocalizations of dihydro pyrazine ring, and can provide 2 electricity by form negative electrical charge Son, provides 2 electronics and provides an electronics by the electronics of reduction addition, to produce 5 electronics altogether by double bond.These freedom Base anion configuration is being shown above in for the formula 2 of N- trialkylsilkl dihydro pyrazines.
While not wishing to it is bound by theory, inventors believe that because dihydro pyrazine part and its anion are non-aromatic , so they are not hindered by their corresponding amine by hydrogen reduction by the loss of fragrant stability, and should also reason its with Ruthenium or other metal-complexings and be catalyzed.Once reduction, it will can not provide stability to dihydro pyrazine part to metal again, then The metal can transfer to be reduced to its metallic state.
According to Chemistry Literature (D.Gopal etc.,Tetrahedron Letters,39,1877-1880,1998)(“Gopal Deng "), it is in terms of a brilliance of the complex of the disclosure, such dihydro pyrazine described herein, or with dialkyl group substitution 3 quaternary carbons alkyl substitution, by ring outside deprotonation produce thermally labile anion, the negative electrical charge of the anion The not delocalization around dihydro pyrazine basic ring, as shown in following formula 4.By contrast, applicant is alkyl-substituted illustrated herein Dihydro pyrazine the deprotonation of bridged ring part can easily be realized and produce anion, the negative electrical charge of the anion is across dihydro Five atom delocalizations of pyrazine basic ring, as shown in Equation 5, the anion for generating in addition is heat-staple." Gopal etc. " document Also reported when dihydro pyrazine is stored at -15 DEG C and dimerization occurs.However, applicant has now been found that 2,2- dihydro -3,3- bis- Methyl -5,6- diethyl pyrazines are at room temperature stable.Additionally, the cooperation of ruthenium and cobalt based on dihydro pyrazine described herein Thing is also stabilization.Applicant now also found, (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) (tetrahydrofuran) Potassium by separating it into as crystalline solid is heat-staple at room temperature, and it is that η -5 matches somebody with somebody to demonstrate it by X-ray crystallography Positioned at potassium (+1), as shown in Figure 5.In a word, the heat endurance of dihydro pyrazine described herein and its bridged ring deprotonation is provided Stabilization and the completely anion of delocalization, stabilization and volatile metal complex can be prepared by the anion.Equally, herein Describe N- alkyl dihydro pyrazine and N- trialkylsilkl dihydro pyrazines, inventors believe that they also will provide stabilization and Volatile metal complex.
Metal dihydride pyrazinyl complex as herein described or composition are preferably highly suitable as ALD, CVD, arteries and veins The volatile precursor of CVD, plasma enhancing ALD (PEALD) or plasma enhanced CVD (PECVD) is rushed to prepare semiconductor The microelectronic component of type, is such as used to store micro- capacity cell (microcapacitor cell) of application (such as DRAM device).Institute Complex is stated to be also very suitable for for preparing thermal detector (pyrodetector) device.For being formed containing metal film or coating Method is preferably depositing operation.Example for the suitable deposition processes of method disclosed herein includes, but are not limited to cyclic cvd (CCVD), MOCVD (metallorganic CVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition (" PECVD "), height Density PECVD, photon assisted CVD, plasma-photon auxiliary (" PPACVD "), low temperature chemical vapor deposition, chemistry auxiliary gas Mutually deposition, hot-wire chemical gas-phase deposition, the CVD of liquid polymer precursor, by supercritical fluid deposition and low energy CVD (LECVD).In some embodiments, containing metal film by ald (ALD), plasma enhancing ALD (PEALD) or Plasma enhancing cyclic cvd (PECCVD) technique is deposited.As used in this article, term " chemical vapor deposition method " Refer to that wherein substrate is exposed to one or more volatile precursor, the precursor reacts and/or decomposes to produce on the surface of a substrate Any technique of the desired deposition of life.As used in this article, term " atom layer deposition process " refers to deposit to material membrane (such as the amount of the membrane material deposited in each reaction cycle is constant) continuous table of self-limited type on the substrate of various compositions Face chemistry.Although precursor used herein, reagent and source there may come a time when to be described as " gas ", it should be understood that precursor can be Liquid or solid, it by directly evaporation, bubbling or distillation in the case of being with or without inert gas in reactor is transported to. In some cases, the precursor of gasification can be by plasma generator.In one embodiment, used containing metal film ALD process deposits.In another embodiment, CCVD process deposits are used containing metal film.In further embodiment, Hot CVD process deposits are used containing metal film.Term " reactor " used herein includes but is not limited to reative cell or settling chamber.
In some embodiments, method disclosed herein is by using before being incorporated into reactor and/or period ALD the or CCVD methods that precursor is separated avoid the pre-reaction of metal precursor.On this point, such as ALD or CCVD techniques Deposition technique be used for deposit dielectric film.In one embodiment, the film is alternately exposed to one by by substrate surface Kind or various metals dihydro pyrazine basigamy polymer composition, oxygen source, reducing agent and/or other precursors or reagent and via ALD works Skill is deposited.Film grows through the pulse length and depositing temperature of self-limited type control, each precursor or the reagent of surface reaction and carries out. Once however, the surface saturation of substrate, film growth stopping.
Depending on deposition process, in some embodiments, one or more metal dihydride pyrazinyl complex can be with Predetermined molal volume or about 0.1 to about 1000 micromole is introduced into reactor.In this implementation method or other embodiment In, metal dihydride pyrazinyl complex precursor can be introduced into reactor with predetermined time span.In some embodiments, The time span is for about 0.001 to about 500 second.
In some embodiments, the film for being deposited using method described herein uses oxygen source, oxygen containing reagent or precursor Formed in the presence of oxygen.Can exist during oxygen source can be introduced into reactor in the form of at least one oxygen source and/or by way of parenthesis In other precursors for deposition process.Suitable oxygen source gas can include such as water (H2O) (for example, deionized water, pure Change water and/or distilled water), oxygen (O2), oxygen plasma, ozone (O3)、NO、NO2, carbon monoxide (CO), carbon dioxide (CO2) And combinations thereof.In some embodiments, oxygen source is included with about 1 to about 2000 sccm (sccm) or about 1 Flow velocity to about 1000sccm is introduced into oxygen source gas in reactor.Oxygen source can introduce the time of about 0.1 to about 100 second. In one specific implementation method, oxygen source is 10 DEG C or water higher comprising temperature.Film passes through ALD or cyclic cvd work wherein In the implementation method of skill deposition, precursor pulse can have more than pulse duration of 0.01 second, and oxygen source can have and be more than The pulse duration of 0.01 second, and the aquapulse duration can have the pulse duration more than 0.01 second.Another In individual implementation method, the purging duration between pulse may be as little to 0 second or can therebetween not had using continuous pulse There is purging.
In some embodiments, this technique uses reducing agent.Reducing agent is generally introduced in gaseous form.Suitable reduction The example of agent includes, but are not limited to hydrogen, hydrogen plasma, long-range hydrogen plasma, silanes (such as diethylsilane, second Base silane, dimethylsilane, phenyl silane, monosilane, disilane, amino silane, chlorosilane), boranes (such as monoborane, Diborane), aluminium alkanes, germane class, hydrazine, ammonia or its mixture.
Deposition process disclosed herein can include one or more purge gas.For purging the reactant not consumed And/or the purge gas of byproduct of reaction are inert gases not with precursors reaction.Exemplary purge gas include, but do not limit In argon (Ar), nitrogen (N2), helium (He), neon, hydrogen (H2) and its mixture.In some embodiments, purge gas such as Ar is with about 10 Flow velocity to about 2000sccm is fed to about 0.1 to 1000 second in reactor, so as to purge unreacted material and may retain Any accessory substance in the reactor.
Each step of supply precursor, oxygen source and/or other precursors, source gas and/or reagent can be used for by changing Supply their time to carry out, to change the stoichiometric composition of generated film.
Energy supply to precursor, containing oxygen source, reducing agent, other precursors or its combination at least one with induced reaction simultaneously Formed on substrate and contain metal film or coating.This kind of energy can be by (but not limited to) heat, plasma, pulse plasma Body, Helicon wave plasma, high-density plasma, inductively coupled plasma, X-ray, electron beam, photon, long-range etc. from Daughter method and combinations thereof is provided.In some embodiments, the 2nd RF radio frequency sources can be used for changing at substrate surface Plasma characteristics.Deposition is related in the implementation method of plasma wherein, and plasma method for generation can include direct Plasma method for generation (its plasma directly occurs in the reactor) or remote plasma as an alternative Body method for generation (its plasma occur outside reactor and be fed to reactor in).
Metal dihydride pyrazinyl complex precursor can in several ways be delivered to reative cell such as CVD or ALD reactors In.In one embodiment, it is possible to use liquid delivery system.In alternative implementation method, can be using united Liquid delivery and flash distillation process unit, such as by Shoreview, the turbine evaporator of the MSP Corporation manufactures of MN, with Make it possible to quantitatively deliver low volatility materials, it causes repeatable conveying and is deposited without the thermal decomposition of precursor.This Shen Please described in precursor composition can effectively be used as source reagent in DLI patterns and matched somebody with somebody with providing these metal dihydride pyrazinyls The steam of polymer precursor is flowed in ALD or CVD reactors.
In some embodiments, these compositions using varsol those, because varsol can be done The dry water to sub- ppm level, they are especially desirable.The exemplary varsol that can be used in the present invention includes, but not It is limited to toluene, mesitylene, cumene (cumene), P-Cymene (4- isopropyl toluenes), 1,3- diisopropyls Benzene, octane, dodecane, 1,2,4- trimethyl-cyclohexanes, n-butyl cyclohexane and decahydronaphthalene (naphthalane).The combination of precursors of the application Thing can also be stored and used in rustless steel container.In some embodiments, the varsol in composition is higher boiling Solvent or with 100 DEG C or boiling point higher.The metal dihydride pyrazinyl complex precursor composition of the application can also be with it Its suitable metal precursor mixing, and the mixture is used to deliver simultaneously two kinds of metals to grow binary metal oxide or nitridation Thing film.
In some embodiments, the purity level of precursor composition it is sufficiently high be for reliable semiconductor manufacturing can Receive.In some embodiments, the precursor containing metal described herein and the composition comprising the precursor are comprising less than 2% Weight or less than 1% weight or less than one or more impurity less than 0.5% weight：Unhindered amina, free halide or halogen The material of ion and higher molecular weight.The higher degree level of metal dihydride pyrazinyl complex precursor described herein can lead to Less than one or more technique is crossed to obtain：Purifying, absorption and/or distillation.
In some embodiments, the gas line that reative cell is connected to from precursor tank requires heat to one according to technique Or multiple temperature, and the container comprising said composition be maintained at for bubbling one or more at a temperature of.In other embodiment party In formula, the composition comprising metal dihydride pyrazinyl complex precursor is expelled to and is maintained at one or more for direct liquid note In evaporator at a temperature of penetrating.
The air-flow of argon and/or other gases can serve as carrier gas to help deliver at least one set of during precursor pulse The steam of metal dihydride pyrazinyl complex precursor is in reative cell.In some embodiments, reative cell processing pressure is for about 1 Support (130Pa).
In typical ALD or CCVD techniques, heated on substrate such as silicon oxide substrate warm table in the reaction chamber, reaction Room starting is exposed to metal dihydride pyrazinyl complex precursor to allow coordination chemistry to be adsorbed onto on the surface of substrate.
Purge gas such as argon gas purges unadsorbed excessive complex from process chamber.After fully purging, can containing nitrogen source Reacted with the surface with absorption with being introduced into reative cell, then purged by another gas and remove reaction by-product with from reative cell Thing.Processing cycle can repeat to obtain desired film thickness.
In this implementation method or other embodiment, it is to be appreciated that can be with the step of method described herein Various orders are carried out, and serially or simultaneously can be entered (such as during at least a portion of another step) and its with being combined OK.The corresponding steps of supply precursor and nitrogen containing source gas can be carried out by changing for supplying their duration, with Change the stoichiometric composition of gained dielectric film.
In another implementation method of method disclosed herein, metal or metal oxide film use ALD deposition method shape Into it is comprised the following steps：
Substrate is provided in the reactor；
Contain metal dihydride comprising formula 3A, 3B of being selected from, the compound of 3C, 3D, 3E or its combination to being introduced in reactor The composition of the precursor of pyrazinyl complex；
The precursor chemical containing metal dihydride pyrazinyl complex is adsorbed on substrate；
The unreacted precursor containing metal dihydride pyrazinyl complex metal is purged using purge gas；
By oxygen source provide to heating substrate on the precursor containing metal dihydride pyrazinyl complex metal with inhaled Attached at least one precursors reaction containing metal dihydride pyrazinyl complex；With
Optionally purge any unreacted oxygen source.
In the further embodiment of method disclosed herein, metal film is formed using ALD deposition method on substrate, Wherein described film has thickness, and methods described includes：
A. it is introduced into comprising selected from least one metal dihydride in formula 3A, 3B, the compound of 3C, 3D, 3E or its combination Pyrazinyl complex；
B. the metal dihydride pyrazinyl coordination chemistry is adsorbed on the substrate；
C. metal dihydride pyrazinyl complex is purged using purge gas；
D. optionally by reducing agent provide to heating substrate on the metal dihydride pyrazinyl complex with inhaled Attached metal dihydride pyrazinyl complex reaction；With
E. optionally purge any unreacted reducing agent, and wherein described reducing agent can selected from hydrogen, hydrogen etc. from Daughter, ammonia, ammonia plasma treatment, hydrogen/nitrogen plasma, alkyl silane and its mixture and wherein repeat step a to e are until obtain Obtain desired thickness of metal film.
Above-mentioned steps define a circulation of method described herein；And the circulation can repeat desired until obtaining Film thickness.In this implementation method or other embodiment, it is possible to understand that can be with various the step of method described herein Order is carried out, and serially or simultaneously can be carried out (such as during at least a portion of another step) and its with being combined. Each step of supply precursor and oxygen source can be carried out by changing for supplying their duration, be situated between with changing gained The stoichiometric composition of electrolemma, although oxygen is always used with the amount less than the stoichiometry relative to available silicon.
For thin multicomponent films, other precursors containing nitrogen precursor, reducing agent or other reagents as containing silicon precursor, can alternately drawn In entering reative cell.
In the further embodiment that method is described herein, dielectric film uses hot CVD process deposits.In the embodiment party In formula, methods described includes：
One or more substrates are placed in and are heated to environment temperature at a temperature of about 700 DEG C and being maintained at 1 support (130Pa) Or in the reactor under lower pressure；
It is introduced into comprising containing selected from least one metal two in formula 3A, 3B, the compound of 3C, 3D, 3E or its combination The composition of hydrogen pyrazinyl complex；With
There is provided oxygen source in reactor with least in part with the reaction of metal dihydride pyrazinyl complex and deposited metal film Onto one or more substrates.In some implementation methods of CVD method, reactor is maintained at 100 in step process is introduced into Under millitorr to the pressure of 600 millitorrs (13 to 80Pa).
Above-mentioned steps define a circulation of method described herein；And the circulation can repeat desired until obtaining Film thickness.In this implementation method or other embodiment, it is possible to understand that can be with various the step of method described herein Order is carried out, and serially or simultaneously can be carried out (such as during at least a portion of another step) and its with being combined. Each step of supply precursor and oxygen source can be carried out by changing for supplying their duration, be situated between with changing gained The stoichiometric composition of electrolemma.
For thin multicomponent films, other precursors as containing silicon precursor, can be with containing nitrogen precursor, oxygen source, reducing agent and/or other reagents It is alternately introduced in reative cell.
Method this document describes metal film is contained by ALD or CVD deposition, including using comprising above-mentioned metal of the present invention The composition of dihydro pyrazine basigamy polymer precursor.In a specific implementation method, there is provided by using DLI delivering and incite somebody to action Composition comprising metal dihydride pyrazinyl complex precursor and compatible solvent is delivered in reative cell, then uses 0.001- The reactor pressure and 0-1000 DEG C of temperature of 1000 supports (0.13-130kPa) aoxidize it with selected from water, alcohol, oxygen, ozone, one The oxygen source reaction of phenodiazine, nitrogen dioxide, hydrogen peroxide or its combination deposits the method containing metal film to grow containing metal film.Take Certainly in the characteristic of metal, the method causes every about 1 angstrom of circulationOr more metal oxide deposition.
The present invention still grows dielectric using one or more metal dihydride pyrazinyl complex precursor described herein The method of film or metal film, so as to be formed selected from dynamic random access memory (DRAM) memory component (memory cell) With the microelectronic component of measurement device.
As an alternative, the present invention is manufactured selected from following microelectronic component using root architecture containing imidazoles of the invention Method：Non-volatile ferroelectric microelectronic memory device, the display phosphors for electroluminescent display, high Tc superconductor device Part.
In a further embodiment, the present invention is the method by ALD or CVD growth metal oxide or nitride film, It includes：Offer is dissolved in the metal dihydride pyrazinyl in the solvent selected from ether, amino ethers, acid amides, ester, fragrance or varsol Complex simultaneously delivers resulting composition to provide the vapor stream of resulting composition by DLI systems, so as to be given birth to by ALD or CVD Metal oxide long or nitride film.
Embodiment
Embodiment 1：The synthesis of 2,2- dihydros -3,3- dimethyl -5,6- diethyl pyrazines (HDMDEP)
3, the 4- acetyl butyryls of 50.0g (0.438 mole) are dissolved in 250 milliliters of tetrahydrofurans of (ml) (THF), are added The H of 38.6g (0.438 mole)2NC(Me)2CH2NH2, stirring was more than 30 minutes and is cooled with an ice bath and is maintained at 20-25 DEG C.Then The mixture was stirred overnight.Then mixture is stirred overnight together with the anhydrous magnesium sulfate of 20 grams (g), filtered, removed with vacuum THF is removed to produce golden yellow liquid (58g).Then 20g dry molecular sieves upper 2 day is placed it into.Then the molecular sieve is removed, and By raw material, bottle is shifted to bottle (bulb-to-bulb) under 65 DEG C/100 millitorrs (13Pa), and the final product of collection is pole light yellow green Liquid.Product yield is 47g (65%).Gas chromatography-mass spectrum (GCMS) shows parent ion in 166mu.
Embodiment 2：(pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium (Cp*RuDMDEP) synthesis
Under the argon atmospher of ventilation, 9.3g (0.056 mole) HDMDEP (embodiment 1) of 20ml tetrahydrofurans will be dissolved in It was added dropwise to be dissolved in 10.66g (0.053 mole) hexamethyl for the 200ml tetrahydrofurans for being cooled to -78 DEG C in 10 minutes In disilazane potassium.The mixture of generation is stirred 30 minutes at -78 DEG C, it was slowly warmed to room temperature through two hours. Then the KDMDEP solution that will be generated adds chlorine (pentamethylcyclopentadiene base) ruthenium (+2) of 14.25g for effective 20 minutes via set In tetramer (RuCp*Cl) (0.052 mole of ruthenium), stirred in 300ml tetrahydrofurans at room temperature.Then mixture is flowed back 2 days.Then be removed in vacuum solvent and under argon gas add 300ml hexanes.The mixture that will be generated vibrates 20 minutes and then mistake Filter to produce dark brown filtrate.With hexane is removed in vacuum to produce dark brown tar.Then by the tar in 140 DEG C/100 millitorrs Bottle distills to bottle under (13Pa) pressure, and to produce golden yellow liquid, it produced crystalline agglomerate through the time solidification of 2 days.Will be upper Layer clear liquid is transferred to -20 DEG C of household freezer 3 days, produces second batch crystal.Then this two batches crystal is merged, then at 140 DEG C Vacuum distillation, discards the first cut as the excessive dihydro pyrazine of trace, then collects as the main of golden brown grease Cut, it was solidified into golden brown crystal through the time of 2 days.Yield=11.0g (52%).54 DEG C of fusing point, TGA shows 2.08 weights The residue of % is measured, as shown in Figure 2.X-ray crystallography confirms that structure is monomer Cp*Ru (DMDEP).
1H NMR:(500MHz, D8 toluene):δ=0.42 (s, 3H), δ=1.14 (t, 3H), δ=1.44 (s, 3H), δ= 1.45 (t, 3H), δ=1.67 (s, 15H), δ=2.4-2.5,2.7-2.8 (m, 4H), δ=3.67 (s, 1H).GCMS displays it is female from Son is in 401mu.
Embodiment 3：(pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) cobalt (Cp* CoHDMDEP synthesis)
Under nitrogen atmosphere, the pentamethylcyclopentadiene of 0.68g (0.005 mole) is added into the 0.2g in 20ml THF In (0.005 mole) hydrofining, mixture be heated up under a nitrogen 45 DEG C 2 hours to produce light yellow suspension.It is subsequently adding The cobaltous dichloride of 0.65g (0.005 mole), mixture is stirred at room temperature overnight to produce dark brown mixture.Add dissolving 1.02g (0.005 mole) KDMDEP (THF) solid in 5ml THF (embodiment 4), the mixture was stirred overnight.Then it is true Sky removes THF, extracts dark oil agglomerate with 30ml hexanes and filters.With being removed in vacuum hexane, and by the dark brown oil Bottle distills to bottle under 120 DEG C/100 millitorrs (13Pa), initially to produce rufous grease, be followed by profound red crystalline product Thing.Yield=0.4g (22%), 126.5 DEG C of fusing point, TGA shows the residue of 8.12 weight %, as shown in Figure 4.GCMS shows Parent ion is in 360mu.1H NMR:(500MHz, D8 toluene):δ=0.95 (s, 3H), δ=0.97 (s, 3H), δ=1.01 (t, 3H), δ=1.42 (t, 3H), δ=1.45 (m, 1H), δ=1.71 (s, 15H), δ=1.73 (m, 1H), δ=2.20 (m, 1H), δ =2.4 (m, 1H), δ=3.29 (s, 1H).
X-ray crystallography confirms that structure is monomer CoCp* (HDMDEP), wherein Co1 with the C12 of η -4 coordinations and HDMDEP, N2, C13 and C14 bonding.
Embodiment 4：(2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) (tetrahydrofuran) potassium be (KDMDEP's THF solution) synthesis
Under an argon, the 5ml THF solutions of 1.7g (0.01 mole) HDMDEP (embodiment 1) were added to through 2 minutes Stirred 90 minutes in the 30ml THF solutions of 1.8g (0.0090 mole) KHMDZ on dry ice and on dry ice, be then warmed to Room temperature 90 minutes.The HDMDEP of solvent, HMDS and non-deprotonation is removed under vacuo to produce thick solid.So Sample is suspended in the hexane of boiling afterwards and is added dropwise over THF until suspension dissolves.Formd when room temperature is cooled to thin Small crystals, it is passed through X-ray crystallography (Fig. 5) and is shown as desired 2,2- dihydro -3 being coordinated with η -5 and potassium, 3- dimethyl - 5,6- diethyl pyrazine base anion, wherein K1 and C9, N1, C12, C11 and N2 bonding.One molecule of THF also with each potassium Ion coordination.For NMR samples, all of THF is extracted out, and sample is prepared in deuterated tetrahydrofuran.1H NMR: (500MHz,D8 THF):δ=0.78 (s, 6H), δ=0.94 (t, 3H), δ=1.04 (t, 3H), δ=2.03 (q, 2H), δ= 2.31 (q, 2H), δ=4.85 (s, 1H).
Embodiment 5：The synthesis of (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) (benzene) ruthenium
The 5ml THF solutions of 1.33g (0.006 mole) HDMDEP (embodiment 1) are added to 1.6g at -78 DEG C In the 50ml THF solutions of (0.0054 mole) hexamethyl phenodiazine silane potassium, it is then set to be warmed to room temperature through 2 hours (hr).So The solution is added into 1.0g (0.004 mole of ruthenium) RuCl afterwards2In the 50ml THF solutions of-benzene.Mixture is flowed back 8 hours, so Remove solvent under vacuo afterwards, the agglomerate of generation is extracted and filtered with 100ml hexanes.Hexane is removed under vacuo, by what is generated Brown oil bottle under 150 DEG C/100 millitorrs (13Pa) distills to generation golden brown oily distillate to bottle.GCMS shows Ru (HDMEP) (benzene) parent ion is in 346mu.
Embodiment 6：RuCp*DMDEP is used as precursor and oxygen as reagent the deposit ruthenium metal under the conditions of ALD
Use the ALD reactors of CN-1 shower header types, the silicon wafer coated in titanium oxide and titanium nitride under the conditions of ALD Upper growth ruthenium film.The process cycles for being used be 50sccm argon gas at 138 DEG C bubbling pass through RuCp*DMDEP (embodiments 2)/600sccm argon gas purging/100sccm oxygen/600sccm argon gas purging, uses the circulation time of 5/20/5/20 second respectively. The argon purging of 600sccm is purged precursor pipeline by 300sccm and 300sccm purging reagent pipelines are constituted.300 DEG C of chip temperature, The pressure of ALD chamber is 3 supports (400Pa).Repeat the circulation and generate~Ru the films of 15nm for 450 times, its XPS analysis is as shown in Figure 6. SIMS (SIMS) analysis to 300 ruthenium films of process cycles growth under the same conditions shows the level of carbon and oxygen Less than 1.0 atom %.
Using with described in embodiment hereof 6 same process condition (for example, at 300 DEG C use RuCp*DMDEP/ Oxygen), the ruthenium film of 9.3 nanometers (nm) is also grown on TiN substrates, and analyzed with AFM (AFM).It was found that region is The ruthenium film of the μ m 6.32nm of 1.00 μ m 1.00 has the RMS of low surface roughness or the 0.31nm determined by AFM.

Claims (12)

1. composition, it includes one or more and matches somebody with somebody selected from dihydro pyrazine base or the metal of dihydro pyrazine with following formula 3A to 3H Compound：
Wherein, in each of formula 3A to 3C, R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or ring-type alkane Base；R5Independently selected from H atom and C1-C6Straight chain, side chain or cyclic alkyl；(L) it is selected from cyclopentadienyl group, five alkyl rings penta Dialkylene, dimethylcyclo-pentadienyl, front three cyclopentadienyl group, methyl cyclopentadienyl, ethyicydopentadi etanyf group, imidazoles The anion of base, trialkylimidazolium base, pyrrole radicals and alkyl pyrrole radicals；M is divalent metal, selected from Fe, Co, Ni, Mn, Ru, Rh, One or more in Pd, Ir and Pt；X=1 or 2；X+y=2；X is independently selected from H atom, C1-C6Straight chain, side chain or ring-type alkane Base and SiR6And wherein R6Independently selected from C1-C3Straight or branched alkyl；
Wherein, in formula 3D, R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or cyclic alkyl；R5Independently select From H atom and C1-C6Straight chain, side chain or cyclic alkyl；(L) it is selected from cyclopentadienyl group, five alkyl cyclopentadienyls, dimethyl Cyclopentadienyl group, front three cyclopentadienyl group, methyl cyclopentadienyl, ethyicydopentadi etanyf group, imidazole radicals, trialkylimidazolium The anion of base, pyrrole radicals and alkyl pyrrole radicals；M is monovalent metal, selected from Fe, Co, Ni, Mn, Ru, Rh, Pd, Ir and Pt One or more；X=1；Y=1 or 2；Z is independently selected from H atom, C1-C6Straight chain, side chain or cyclic alkyl and SiR6, its Middle R6Independently selected from C1-C6Straight or branched alkyl；
Wherein, in formula 3E, R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or cyclic alkyl；R5Independently select From H atom and C1-C6Straight chain, side chain or cyclic alkyl；(Q) benzene and alkylated benzenes are selected from；M is metal, selected from Fe, Co, Ni, Mn, One or more in Ru, Rh, Pd, Ir and Pt；X is 1 or 2；Y=1；With Z independently selected from H atom and C1-C6Straight or branched Alkyl or ring-type C3-C6Alkyl and SiR6, wherein R6It is C1-C3Straight or branched alkyl；
Wherein, in each of formula 3F to 3H, R1、R2、R3And R4It is each independently selected from C1-C6Straight chain, side chain or ring-type alkane Base；R5Independently selected from H atom and C1-C6Straight chain, side chain or cyclic alkyl；(Q) it is benzene or alkylated benzenes；M is monovalent metal, One or more in selected from Fe, Co, Ni, Mn, Ru, Rh, Pd, Ir and Pt；Y=1；X is independently selected from H atom, C1-C6Straight chain, Side chain or cyclic alkyl and SiR6And wherein R6Independently selected from C1-C3Straight or branched alkyl.
2. the composition described in claim 1, wherein the metal complex is free of oxygen atom.
3. the composition described in claim 1 or claim 2, wherein the dihydro pyrazine part is 2,2- dihydro -3,3- Dimethyl -5,6- diethyl pyrazines, or the dihydro pyrazine ylidene ligands are 2,2- dihydro -3,3- dimethyl -5,6- diethyl Pyrazinyl.
4. the composition described in claim 1 or claim 2, wherein the metal is ruthenium or cobalt.
5. the composition described in claim 1 or claim 2, wherein L is pentamethylcyclopentadiene base (Cp*).
6. the composition described in claim 1 or claim 2, wherein the metal complex be selected from it is following at least one Kind：(pentamethylcyclopentadiene base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines base) ruthenium, (pentamethylcyclopentadiene Base) (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrazines) cobalt, (2,2- dihydro -3,3- dimethyl -5,6- diethyl pyrroles Piperazine) (benzene) ruthenium, and combinations thereof.
7. the method containing metal film is formed on substrate, wherein the film has thickness, methods described includes：
A. the composition comprising at least one metal complex as any one of claim 1 to 6 is introduced；
B. by the metal complex chemisorbed to the substrate；
C. the metal complex is purged using purge gas.
8. the method described in claim 7, for forming metal oxide film on substrate, methods described also includes：
D. by oxygen source provide to heating substrate on the metal complex with the group containing the metal complex for having adsorbed Compound reacts；With
E. any unreacted oxygen source is optionally purged.
9. the method described in claim 7, for forming metal film on substrate, methods described also includes：
D. the metal complex to the substrate of heating is provided by reducing agent to be reacted with the metal complex for being adsorbed；With
E. any unreacted reducing agent is optionally purged.
10. the method described in claim 9, wherein the reducing agent be selected from hydrogen, hydrogen plasma, ammonia, ammonia plasma treatment, hydrogen/ Nitrogen plasma, alkyl silane and its mixture.
Method any one of 11. claims 7 to 10, wherein repeat step a to d and optional step e are until form Described film thickness.
Method any one of 12. claims 7 to 10, wherein methods described are atom layer deposition process.
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Families Citing this family (221)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130023129A1 (en) 2011-07-20 2013-01-24 Asm America, Inc. Pressure transmitter for a semiconductor processing environment
US10714315B2 (en) 2012-10-12 2020-07-14 Asm Ip Holdings B.V. Semiconductor reaction chamber showerhead
US20160376700A1 (en) 2013-02-01 2016-12-29 Asm Ip Holding B.V. System for treatment of deposition reactor
US9994954B2 (en) * 2013-07-26 2018-06-12 Versum Materials Us, Llc Volatile dihydropyrazinly and dihydropyrazine metal complexes
JP6209176B2 (en) 2014-04-14 2017-10-04 オークマ株式会社 Position control device
US10941490B2 (en) 2014-10-07 2021-03-09 Asm Ip Holding B.V. Multiple temperature range susceptor, assembly, reactor and system including the susceptor, and methods of using the same
US10276355B2 (en) 2015-03-12 2019-04-30 Asm Ip Holding B.V. Multi-zone reactor, system including the reactor, and method of using the same
US10458018B2 (en) 2015-06-26 2019-10-29 Asm Ip Holding B.V. Structures including metal carbide material, devices including the structures, and methods of forming same
US10211308B2 (en) 2015-10-21 2019-02-19 Asm Ip Holding B.V. NbMC layers
US11139308B2 (en) 2015-12-29 2021-10-05 Asm Ip Holding B.V. Atomic layer deposition of III-V compounds to form V-NAND devices
US10529554B2 (en) 2016-02-19 2020-01-07 Asm Ip Holding B.V. Method for forming silicon nitride film selectively on sidewalls or flat surfaces of trenches
US11453943B2 (en) 2016-05-25 2022-09-27 Asm Ip Holding B.V. Method for forming carbon-containing silicon/metal oxide or nitride film by ALD using silicon precursor and hydrocarbon precursor
US10612137B2 (en) 2016-07-08 2020-04-07 Asm Ip Holdings B.V. Organic reactants for atomic layer deposition
US9859151B1 (en) 2016-07-08 2018-01-02 Asm Ip Holding B.V. Selective film deposition method to form air gaps
US9887082B1 (en) 2016-07-28 2018-02-06 Asm Ip Holding B.V. Method and apparatus for filling a gap
US9812320B1 (en) 2016-07-28 2017-11-07 Asm Ip Holding B.V. Method and apparatus for filling a gap
US11532757B2 (en) 2016-10-27 2022-12-20 Asm Ip Holding B.V. Deposition of charge trapping layers
US10714350B2 (en) 2016-11-01 2020-07-14 ASM IP Holdings, B.V. Methods for forming a transition metal niobium nitride film on a substrate by atomic layer deposition and related semiconductor device structures
KR102546317B1 (en) 2016-11-15 2023-06-21 에이에스엠 아이피 홀딩 비.브이. Gas supply unit and substrate processing apparatus including the same
KR20180068582A (en) 2016-12-14 2018-06-22 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
US11581186B2 (en) 2016-12-15 2023-02-14 Asm Ip Holding B.V. Sequential infiltration synthesis apparatus
US11447861B2 (en) 2016-12-15 2022-09-20 Asm Ip Holding B.V. Sequential infiltration synthesis apparatus and a method of forming a patterned structure
US10269558B2 (en) 2016-12-22 2019-04-23 Asm Ip Holding B.V. Method of forming a structure on a substrate
US11390950B2 (en) 2017-01-10 2022-07-19 Asm Ip Holding B.V. Reactor system and method to reduce residue buildup during a film deposition process
US10468261B2 (en) 2017-02-15 2019-11-05 Asm Ip Holding B.V. Methods for forming a metallic film on a substrate by cyclical deposition and related semiconductor device structures
US10770286B2 (en) 2017-05-08 2020-09-08 Asm Ip Holdings B.V. Methods for selectively forming a silicon nitride film on a substrate and related semiconductor device structures
US12040200B2 (en) 2017-06-20 2024-07-16 Asm Ip Holding B.V. Semiconductor processing apparatus and methods for calibrating a semiconductor processing apparatus
US11306395B2 (en) 2017-06-28 2022-04-19 Asm Ip Holding B.V. Methods for depositing a transition metal nitride film on a substrate by atomic layer deposition and related deposition apparatus
KR20190009245A (en) 2017-07-18 2019-01-28 에이에스엠 아이피 홀딩 비.브이. Methods for forming a semiconductor device structure and related semiconductor device structures
US11374112B2 (en) 2017-07-19 2022-06-28 Asm Ip Holding B.V. Method for depositing a group IV semiconductor and related semiconductor device structures
US10590535B2 (en) 2017-07-26 2020-03-17 Asm Ip Holdings B.V. Chemical treatment, deposition and/or infiltration apparatus and method for using the same
US10692741B2 (en) 2017-08-08 2020-06-23 Asm Ip Holdings B.V. Radiation shield
US10770336B2 (en) 2017-08-08 2020-09-08 Asm Ip Holding B.V. Substrate lift mechanism and reactor including same
US11769682B2 (en) 2017-08-09 2023-09-26 Asm Ip Holding B.V. Storage apparatus for storing cassettes for substrates and processing apparatus equipped therewith
US11830730B2 (en) 2017-08-29 2023-11-28 Asm Ip Holding B.V. Layer forming method and apparatus
US11295980B2 (en) 2017-08-30 2022-04-05 Asm Ip Holding B.V. Methods for depositing a molybdenum metal film over a dielectric surface of a substrate by a cyclical deposition process and related semiconductor device structures
US10658205B2 (en) 2017-09-28 2020-05-19 Asm Ip Holdings B.V. Chemical dispensing apparatus and methods for dispensing a chemical to a reaction chamber
US10403504B2 (en) 2017-10-05 2019-09-03 Asm Ip Holding B.V. Method for selectively depositing a metallic film on a substrate
US10923344B2 (en) 2017-10-30 2021-02-16 Asm Ip Holding B.V. Methods for forming a semiconductor structure and related semiconductor structures
WO2019103610A1 (en) 2017-11-27 2019-05-31 Asm Ip Holding B.V. Apparatus including a clean mini environment
JP7214724B2 (en) 2017-11-27 2023-01-30 エーエスエム アイピー ホールディング ビー．ブイ． Storage device for storing wafer cassettes used in batch furnaces
US10872771B2 (en) 2018-01-16 2020-12-22 Asm Ip Holding B. V. Method for depositing a material film on a substrate within a reaction chamber by a cyclical deposition process and related device structures
TWI799494B (en) 2018-01-19 2023-04-21 荷蘭商Ａｓｍ 智慧財產控股公司 Deposition method
CN111630203A (en) 2018-01-19 2020-09-04 Asm Ip私人控股有限公司 Method for depositing gap filling layer by plasma auxiliary deposition
US11081345B2 (en) 2018-02-06 2021-08-03 Asm Ip Holding B.V. Method of post-deposition treatment for silicon oxide film
US10896820B2 (en) 2018-02-14 2021-01-19 Asm Ip Holding B.V. Method for depositing a ruthenium-containing film on a substrate by a cyclical deposition process
JP7124098B2 (en) 2018-02-14 2022-08-23 エーエスエム・アイピー・ホールディング・ベー・フェー Method for depositing a ruthenium-containing film on a substrate by a cyclical deposition process
KR102636427B1 (en) 2018-02-20 2024-02-13 에이에스엠 아이피 홀딩 비.브이. Substrate processing method and apparatus
US10975470B2 (en) 2018-02-23 2021-04-13 Asm Ip Holding B.V. Apparatus for detecting or monitoring for a chemical precursor in a high temperature environment
US11473195B2 (en) 2018-03-01 2022-10-18 Asm Ip Holding B.V. Semiconductor processing apparatus and a method for processing a substrate
US11629406B2 (en) 2018-03-09 2023-04-18 Asm Ip Holding B.V. Semiconductor processing apparatus comprising one or more pyrometers for measuring a temperature of a substrate during transfer of the substrate
KR102646467B1 (en) 2018-03-27 2024-03-11 에이에스엠 아이피 홀딩 비.브이. Method of forming an electrode on a substrate and a semiconductor device structure including an electrode
US11230766B2 (en) 2018-03-29 2022-01-25 Asm Ip Holding B.V. Substrate processing apparatus and method
US20190309422A1 (en) * 2018-04-06 2019-10-10 Versum Materials Us, Llc Spin-On Metallization
TWI843623B (en) 2018-05-08 2024-05-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Methods for depositing an oxide film on a substrate by a cyclical deposition process and related device structures
US12025484B2 (en) 2018-05-08 2024-07-02 Asm Ip Holding B.V. Thin film forming method
KR102596988B1 (en) 2018-05-28 2023-10-31 에이에스엠 아이피 홀딩 비.브이. Method of processing a substrate and a device manufactured by the same
US11718913B2 (en) 2018-06-04 2023-08-08 Asm Ip Holding B.V. Gas distribution system and reactor system including same
TWI840362B (en) 2018-06-04 2024-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Wafer handling chamber with moisture reduction
US11286562B2 (en) 2018-06-08 2022-03-29 Asm Ip Holding B.V. Gas-phase chemical reactor and method of using same
US10797133B2 (en) 2018-06-21 2020-10-06 Asm Ip Holding B.V. Method for depositing a phosphorus doped silicon arsenide film and related semiconductor device structures
KR102568797B1 (en) 2018-06-21 2023-08-21 에이에스엠 아이피 홀딩 비.브이. Substrate processing system
WO2020003000A1 (en) 2018-06-27 2020-01-02 Asm Ip Holding B.V. Cyclic deposition methods for forming metal-containing material and films and structures including the metal-containing material
TW202409324A (en) 2018-06-27 2024-03-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Cyclic deposition processes for forming metal-containing material
US10612136B2 (en) 2018-06-29 2020-04-07 ASM IP Holding, B.V. Temperature-controlled flange and reactor system including same
US10755922B2 (en) 2018-07-03 2020-08-25 Asm Ip Holding B.V. Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition
US10388513B1 (en) 2018-07-03 2019-08-20 Asm Ip Holding B.V. Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition
EP3821057A1 (en) * 2018-07-12 2021-05-19 Basf Se Process for the generation of metal- or semimetal-containing films
US11430674B2 (en) 2018-08-22 2022-08-30 Asm Ip Holding B.V. Sensor array, apparatus for dispensing a vapor phase reactant to a reaction chamber and related methods
KR102707956B1 (en) 2018-09-11 2024-09-19 에이에스엠 아이피 홀딩 비.브이. Method for deposition of a thin film
US11024523B2 (en) 2018-09-11 2021-06-01 Asm Ip Holding B.V. Substrate processing apparatus and method
TWI844567B (en) 2018-10-01 2024-06-11 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate retaining apparatus, system including the apparatus, and method of using same
US11232963B2 (en) 2018-10-03 2022-01-25 Asm Ip Holding B.V. Substrate processing apparatus and method
KR102592699B1 (en) 2018-10-08 2023-10-23 에이에스엠 아이피 홀딩 비.브이. Substrate support unit and apparatuses for depositing thin film and processing the substrate including the same
KR102605121B1 (en) 2018-10-19 2023-11-23 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus and substrate processing method
KR102546322B1 (en) 2018-10-19 2023-06-21 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus and substrate processing method
US11087997B2 (en) 2018-10-31 2021-08-10 Asm Ip Holding B.V. Substrate processing apparatus for processing substrates
KR20200051105A (en) 2018-11-02 2020-05-13 에이에스엠 아이피 홀딩 비.브이. Substrate support unit and substrate processing apparatus including the same
US11572620B2 (en) 2018-11-06 2023-02-07 Asm Ip Holding B.V. Methods for selectively depositing an amorphous silicon film on a substrate
US10818758B2 (en) 2018-11-16 2020-10-27 Asm Ip Holding B.V. Methods for forming a metal silicate film on a substrate in a reaction chamber and related semiconductor device structures
US12040199B2 (en) 2018-11-28 2024-07-16 Asm Ip Holding B.V. Substrate processing apparatus for processing substrates
US11217444B2 (en) 2018-11-30 2022-01-04 Asm Ip Holding B.V. Method for forming an ultraviolet radiation responsive metal oxide-containing film
KR102636428B1 (en) 2018-12-04 2024-02-13 에이에스엠 아이피 홀딩 비.브이. A method for cleaning a substrate processing apparatus
US11158513B2 (en) 2018-12-13 2021-10-26 Asm Ip Holding B.V. Methods for forming a rhenium-containing film on a substrate by a cyclical deposition process and related semiconductor device structures
JP7504584B2 (en) 2018-12-14 2024-06-24 エーエスエム・アイピー・ホールディング・ベー・フェー Method and system for forming device structures using selective deposition of gallium nitride - Patents.com
JP7246184B2 (en) * 2018-12-27 2023-03-27 東京エレクトロン株式会社 RuSi film formation method
TWI819180B (en) 2019-01-17 2023-10-21 荷蘭商Ａｓｍ 智慧財產控股公司 Methods of forming a transition metal containing film on a substrate by a cyclical deposition process
KR20200091543A (en) 2019-01-22 2020-07-31 에이에스엠 아이피 홀딩 비.브이. Semiconductor processing device
JP2020136678A (en) 2019-02-20 2020-08-31 エーエスエム・アイピー・ホールディング・ベー・フェー Method for filing concave part formed inside front surface of base material, and device
KR20200102357A (en) 2019-02-20 2020-08-31 에이에스엠 아이피 홀딩 비.브이. Apparatus and methods for plug fill deposition in 3-d nand applications
KR102626263B1 (en) 2019-02-20 2024-01-16 에이에스엠 아이피 홀딩 비.브이. Cyclical deposition method including treatment step and apparatus for same
TWI845607B (en) 2019-02-20 2024-06-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Cyclical deposition method and apparatus for filling a recess formed within a substrate surface
TWI842826B (en) 2019-02-22 2024-05-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing apparatus and method for processing substrate
KR20200108242A (en) 2019-03-08 2020-09-17 에이에스엠 아이피 홀딩 비.브이. Method for Selective Deposition of Silicon Nitride Layer and Structure Including Selectively-Deposited Silicon Nitride Layer
US11742198B2 (en) 2019-03-08 2023-08-29 Asm Ip Holding B.V. Structure including SiOCN layer and method of forming same
KR20200116033A (en) 2019-03-28 2020-10-08 에이에스엠 아이피 홀딩 비.브이. Door opener and substrate processing apparatus provided therewith
KR20200116855A (en) 2019-04-01 2020-10-13 에이에스엠 아이피 홀딩 비.브이. Method of manufacturing semiconductor device
US10961624B2 (en) * 2019-04-02 2021-03-30 Gelest Technologies, Inc. Process for pulsed thin film deposition
KR20200123380A (en) 2019-04-19 2020-10-29 에이에스엠 아이피 홀딩 비.브이. Layer forming method and apparatus
KR20200125453A (en) 2019-04-24 2020-11-04 에이에스엠 아이피 홀딩 비.브이. Gas-phase reactor system and method of using same
KR20200130118A (en) 2019-05-07 2020-11-18 에이에스엠 아이피 홀딩 비.브이. Method for Reforming Amorphous Carbon Polymer Film
KR20200130121A (en) 2019-05-07 2020-11-18 에이에스엠 아이피 홀딩 비.브이. Chemical source vessel with dip tube
KR20200130652A (en) 2019-05-10 2020-11-19 에이에스엠 아이피 홀딩 비.브이. Method of depositing material onto a surface and structure formed according to the method
JP2020188254A (en) 2019-05-16 2020-11-19 エーエスエム アイピー ホールディング ビー．ブイ． Wafer boat handling device, vertical batch furnace, and method
JP2020188255A (en) 2019-05-16 2020-11-19 エーエスエム アイピー ホールディング ビー．ブイ． Wafer boat handling device, vertical batch furnace, and method
USD947913S1 (en) 2019-05-17 2022-04-05 Asm Ip Holding B.V. Susceptor shaft
USD975665S1 (en) 2019-05-17 2023-01-17 Asm Ip Holding B.V. Susceptor shaft
KR20200141003A (en) 2019-06-06 2020-12-17 에이에스엠 아이피 홀딩 비.브이. Gas-phase reactor system including a gas detector
KR20200143254A (en) 2019-06-11 2020-12-23 에이에스엠 아이피 홀딩 비.브이. Method of forming an electronic structure using an reforming gas, system for performing the method, and structure formed using the method
CN110128373B (en) * 2019-06-12 2023-03-24 鸿翌科技有限公司 Piperazinyl tin complex, preparation method thereof, thin film and solar cell
USD944946S1 (en) 2019-06-14 2022-03-01 Asm Ip Holding B.V. Shower plate
KR20210005515A (en) 2019-07-03 2021-01-14 에이에스엠 아이피 홀딩 비.브이. Temperature control assembly for substrate processing apparatus and method of using same
JP7499079B2 (en) 2019-07-09 2024-06-13 エーエスエム・アイピー・ホールディング・ベー・フェー Plasma device using coaxial waveguide and substrate processing method
CN112216646A (en) 2019-07-10 2021-01-12 Asm Ip私人控股有限公司 Substrate supporting assembly and substrate processing device comprising same
KR20210010307A (en) 2019-07-16 2021-01-27 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
JP7296806B2 (en) 2019-07-16 2023-06-23 東京エレクトロン株式会社 RuSi film forming method and substrate processing system
KR20210010816A (en) 2019-07-17 2021-01-28 에이에스엠 아이피 홀딩 비.브이. Radical assist ignition plasma system and method
KR20210010820A (en) 2019-07-17 2021-01-28 에이에스엠 아이피 홀딩 비.브이. Methods of forming silicon germanium structures
US11643724B2 (en) 2019-07-18 2023-05-09 Asm Ip Holding B.V. Method of forming structures using a neutral beam
TWI839544B (en) 2019-07-19 2024-04-21 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming topology-controlled amorphous carbon polymer film
KR20210010817A (en) 2019-07-19 2021-01-28 에이에스엠 아이피 홀딩 비.브이. Method of Forming Topology-Controlled Amorphous Carbon Polymer Film
CN112309843A (en) 2019-07-29 2021-02-02 Asm Ip私人控股有限公司 Selective deposition method for achieving high dopant doping
CN112309900A (en) 2019-07-30 2021-02-02 Asm Ip私人控股有限公司 Substrate processing apparatus
CN112309899A (en) 2019-07-30 2021-02-02 Asm Ip私人控股有限公司 Substrate processing apparatus
US11587815B2 (en) 2019-07-31 2023-02-21 Asm Ip Holding B.V. Vertical batch furnace assembly
US11227782B2 (en) 2019-07-31 2022-01-18 Asm Ip Holding B.V. Vertical batch furnace assembly
US11587814B2 (en) 2019-07-31 2023-02-21 Asm Ip Holding B.V. Vertical batch furnace assembly
CN118422165A (en) 2019-08-05 2024-08-02 Asm Ip私人控股有限公司 Liquid level sensor for chemical source container
USD965044S1 (en) 2019-08-19 2022-09-27 Asm Ip Holding B.V. Susceptor shaft
USD965524S1 (en) 2019-08-19 2022-10-04 Asm Ip Holding B.V. Susceptor support
JP2021031769A (en) 2019-08-21 2021-03-01 エーエスエム アイピー ホールディング ビー．ブイ． Production apparatus of mixed gas of film deposition raw material and film deposition apparatus
USD940837S1 (en) 2019-08-22 2022-01-11 Asm Ip Holding B.V. Electrode
USD979506S1 (en) 2019-08-22 2023-02-28 Asm Ip Holding B.V. Insulator
USD949319S1 (en) 2019-08-22 2022-04-19 Asm Ip Holding B.V. Exhaust duct
KR20210024423A (en) 2019-08-22 2021-03-05 에이에스엠 아이피 홀딩 비.브이. Method for forming a structure with a hole
US11286558B2 (en) 2019-08-23 2022-03-29 Asm Ip Holding B.V. Methods for depositing a molybdenum nitride film on a surface of a substrate by a cyclical deposition process and related semiconductor device structures including a molybdenum nitride film
KR20210024420A (en) 2019-08-23 2021-03-05 에이에스엠 아이피 홀딩 비.브이. Method for depositing silicon oxide film having improved quality by peald using bis(diethylamino)silane
KR20210029090A (en) 2019-09-04 2021-03-15 에이에스엠 아이피 홀딩 비.브이. Methods for selective deposition using a sacrificial capping layer
KR20210029663A (en) 2019-09-05 2021-03-16 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
US11562901B2 (en) 2019-09-25 2023-01-24 Asm Ip Holding B.V. Substrate processing method
CN112593212B (en) 2019-10-02 2023-12-22 Asm Ip私人控股有限公司 Method for forming topologically selective silicon oxide film by cyclic plasma enhanced deposition process
KR20210042810A (en) 2019-10-08 2021-04-20 에이에스엠 아이피 홀딩 비.브이. Reactor system including a gas distribution assembly for use with activated species and method of using same
TWI846953B (en) 2019-10-08 2024-07-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing device
KR20210043460A (en) 2019-10-10 2021-04-21 에이에스엠 아이피 홀딩 비.브이. Method of forming a photoresist underlayer and structure including same
US12009241B2 (en) 2019-10-14 2024-06-11 Asm Ip Holding B.V. Vertical batch furnace assembly with detector to detect cassette
TWI834919B (en) 2019-10-16 2024-03-11 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of topology-selective film formation of silicon oxide
US11637014B2 (en) 2019-10-17 2023-04-25 Asm Ip Holding B.V. Methods for selective deposition of doped semiconductor material
KR20210047808A (en) 2019-10-21 2021-04-30 에이에스엠 아이피 홀딩 비.브이. Apparatus and methods for selectively etching films
KR20210050453A (en) 2019-10-25 2021-05-07 에이에스엠 아이피 홀딩 비.브이. Methods for filling a gap feature on a substrate surface and related semiconductor structures
US11646205B2 (en) 2019-10-29 2023-05-09 Asm Ip Holding B.V. Methods of selectively forming n-type doped material on a surface, systems for selectively forming n-type doped material, and structures formed using same
KR20210054983A (en) 2019-11-05 2021-05-14 에이에스엠 아이피 홀딩 비.브이. Structures with doped semiconductor layers and methods and systems for forming same
US11501968B2 (en) 2019-11-15 2022-11-15 Asm Ip Holding B.V. Method for providing a semiconductor device with silicon filled gaps
KR20210062561A (en) 2019-11-20 2021-05-31 에이에스엠 아이피 홀딩 비.브이. Method of depositing carbon-containing material on a surface of a substrate, structure formed using the method, and system for forming the structure
KR20210065848A (en) 2019-11-26 2021-06-04 에이에스엠 아이피 홀딩 비.브이. Methods for selectivley forming a target film on a substrate comprising a first dielectric surface and a second metallic surface
CN112951697A (en) 2019-11-26 2021-06-11 Asm Ip私人控股有限公司 Substrate processing apparatus
CN112885693A (en) 2019-11-29 2021-06-01 Asm Ip私人控股有限公司 Substrate processing apparatus
CN112885692A (en) 2019-11-29 2021-06-01 Asm Ip私人控股有限公司 Substrate processing apparatus
JP7527928B2 (en) 2019-12-02 2024-08-05 エーエスエム・アイピー・ホールディング・ベー・フェー Substrate processing apparatus and substrate processing method
KR20210070898A (en) 2019-12-04 2021-06-15 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
TW202125596A (en) 2019-12-17 2021-07-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming vanadium nitride layer and structure including the vanadium nitride layer
US11527403B2 (en) 2019-12-19 2022-12-13 Asm Ip Holding B.V. Methods for filling a gap feature on a substrate surface and related semiconductor structures
KR20210089079A (en) 2020-01-06 2021-07-15 에이에스엠 아이피 홀딩 비.브이. Channeled lift pin
TW202140135A (en) 2020-01-06 2021-11-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Gas supply assembly and valve plate assembly
US11993847B2 (en) 2020-01-08 2024-05-28 Asm Ip Holding B.V. Injector
KR102675856B1 (en) 2020-01-20 2024-06-17 에이에스엠 아이피 홀딩 비.브이. Method of forming thin film and method of modifying surface of thin film
TW202130846A (en) 2020-02-03 2021-08-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming structures including a vanadium or indium layer
TW202146882A (en) 2020-02-04 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of verifying an article, apparatus for verifying an article, and system for verifying a reaction chamber
US11776846B2 (en) 2020-02-07 2023-10-03 Asm Ip Holding B.V. Methods for depositing gap filling fluids and related systems and devices
US11781243B2 (en) 2020-02-17 2023-10-10 Asm Ip Holding B.V. Method for depositing low temperature phosphorous-doped silicon
TW202203344A (en) 2020-02-28 2022-01-16 荷蘭商Ａｓｍ Ｉｐ控股公司 System dedicated for parts cleaning
KR20210116240A (en) 2020-03-11 2021-09-27 에이에스엠 아이피 홀딩 비.브이. Substrate handling device with adjustable joints
KR20210116249A (en) 2020-03-11 2021-09-27 에이에스엠 아이피 홀딩 비.브이. lockout tagout assembly and system and method of using same
CN113394086A (en) 2020-03-12 2021-09-14 Asm Ip私人控股有限公司 Method for producing a layer structure having a target topological profile
KR20210124042A (en) 2020-04-02 2021-10-14 에이에스엠 아이피 홀딩 비.브이. Thin film forming method
TW202146689A (en) 2020-04-03 2021-12-16 荷蘭商Ａｓｍ Ｉｐ控股公司 Method for forming barrier layer and method for manufacturing semiconductor device
TW202145344A (en) 2020-04-08 2021-12-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Apparatus and methods for selectively etching silcon oxide films
KR20210127620A (en) 2020-04-13 2021-10-22 에이에스엠 아이피 홀딩 비.브이. method of forming a nitrogen-containing carbon film and system for performing the method
KR20210128343A (en) 2020-04-15 2021-10-26 에이에스엠 아이피 홀딩 비.브이. Method of forming chromium nitride layer and structure including the chromium nitride layer
US11821078B2 (en) 2020-04-15 2023-11-21 Asm Ip Holding B.V. Method for forming precoat film and method for forming silicon-containing film
US11996289B2 (en) 2020-04-16 2024-05-28 Asm Ip Holding B.V. Methods of forming structures including silicon germanium and silicon layers, devices formed using the methods, and systems for performing the methods
KR20210132600A (en) 2020-04-24 2021-11-04 에이에스엠 아이피 홀딩 비.브이. Methods and systems for depositing a layer comprising vanadium, nitrogen, and a further element
JP2021172884A (en) 2020-04-24 2021-11-01 エーエスエム・アイピー・ホールディング・ベー・フェー Method of forming vanadium nitride-containing layer and structure comprising vanadium nitride-containing layer
TW202146831A (en) 2020-04-24 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Vertical batch furnace assembly, and method for cooling vertical batch furnace
KR20210134226A (en) 2020-04-29 2021-11-09 에이에스엠 아이피 홀딩 비.브이. Solid source precursor vessel
KR20210134869A (en) 2020-05-01 2021-11-11 에이에스엠 아이피 홀딩 비.브이. Fast FOUP swapping with a FOUP handler
TW202147543A (en) 2020-05-04 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Semiconductor processing system
KR20210141379A (en) 2020-05-13 2021-11-23 에이에스엠 아이피 홀딩 비.브이. Laser alignment fixture for a reactor system
TW202146699A (en) 2020-05-15 2021-12-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming a silicon germanium layer, semiconductor structure, semiconductor device, method of forming a deposition layer, and deposition system
KR20210143653A (en) 2020-05-19 2021-11-29 에이에스엠 아이피 홀딩 비.브이. Substrate processing apparatus
KR20210145078A (en) 2020-05-21 2021-12-01 에이에스엠 아이피 홀딩 비.브이. Structures including multiple carbon layers and methods of forming and using same
KR102702526B1 (en) 2020-05-22 2024-09-03 에이에스엠 아이피 홀딩 비.브이. Apparatus for depositing thin films using hydrogen peroxide
EP4158078A1 (en) 2020-05-27 2023-04-05 Gelest, Inc. Silicon-based thin films from n-alkyl substituted perhydridocyclotrisilazanes
TW202201602A (en) 2020-05-29 2022-01-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing device
TW202212620A (en) 2020-06-02 2022-04-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Apparatus for processing substrate, method of forming film, and method of controlling apparatus for processing substrate
TW202218133A (en) 2020-06-24 2022-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method for forming a layer provided with silicon
TW202217953A (en) 2020-06-30 2022-05-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Substrate processing method
KR102707957B1 (en) 2020-07-08 2024-09-19 에이에스엠 아이피 홀딩 비.브이. Method for processing a substrate
TW202219628A (en) 2020-07-17 2022-05-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Structures and methods for use in photolithography
TW202204662A (en) 2020-07-20 2022-02-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method and system for depositing molybdenum layers
US12040177B2 (en) 2020-08-18 2024-07-16 Asm Ip Holding B.V. Methods for forming a laminate film by cyclical plasma-enhanced deposition processes
KR20220027026A (en) 2020-08-26 2022-03-07 에이에스엠 아이피 홀딩 비.브이. Method and system for forming metal silicon oxide and metal silicon oxynitride
TW202229601A (en) 2020-08-27 2022-08-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of forming patterned structures, method of manipulating mechanical property, device structure, and substrate processing system
USD990534S1 (en) 2020-09-11 2023-06-27 Asm Ip Holding B.V. Weighted lift pin
USD1012873S1 (en) 2020-09-24 2024-01-30 Asm Ip Holding B.V. Electrode for semiconductor processing apparatus
US12009224B2 (en) 2020-09-29 2024-06-11 Asm Ip Holding B.V. Apparatus and method for etching metal nitrides
US11726405B2 (en) * 2020-09-30 2023-08-15 Taiwan Semiconductor Manufacturing Company, Ltd. Photoresist for semiconductor fabrication
KR20220045900A (en) 2020-10-06 2022-04-13 에이에스엠 아이피 홀딩 비.브이. Deposition method and an apparatus for depositing a silicon-containing material
CN114293174A (en) 2020-10-07 2022-04-08 Asm Ip私人控股有限公司 Gas supply unit and substrate processing apparatus including the same
TW202229613A (en) 2020-10-14 2022-08-01 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method of depositing material on stepped structure
KR20220053482A (en) 2020-10-22 2022-04-29 에이에스엠 아이피 홀딩 비.브이. Method of depositing vanadium metal, structure, device and a deposition assembly
TW202223136A (en) 2020-10-28 2022-06-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Method for forming layer on substrate, and semiconductor processing system
TW202235649A (en) 2020-11-24 2022-09-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Methods for filling a gap and related systems and devices
TW202235675A (en) 2020-11-30 2022-09-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Injector, and substrate processing apparatus
US11946137B2 (en) 2020-12-16 2024-04-02 Asm Ip Holding B.V. Runout and wobble measurement fixtures
TW202231903A (en) 2020-12-22 2022-08-16 荷蘭商Ａｓｍ Ｉｐ私人控股有限公司 Transition metal deposition method, transition metal layer, and deposition assembly for depositing transition metal on substrate
JP7112768B2 (en) 2020-12-23 2022-08-04 株式会社クリエイティブコーティングス ALD equipment for metal films
USD1023959S1 (en) 2021-05-11 2024-04-23 Asm Ip Holding B.V. Electrode for substrate processing apparatus
USD980814S1 (en) 2021-05-11 2023-03-14 Asm Ip Holding B.V. Gas distributor for substrate processing apparatus
USD981973S1 (en) 2021-05-11 2023-03-28 Asm Ip Holding B.V. Reactor wall for substrate processing apparatus
USD980813S1 (en) 2021-05-11 2023-03-14 Asm Ip Holding B.V. Gas flow control plate for substrate processing apparatus
USD990441S1 (en) 2021-09-07 2023-06-27 Asm Ip Holding B.V. Gas flow control plate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070054487A1 (en) * 2005-09-06 2007-03-08 Applied Materials, Inc. Atomic layer deposition processes for ruthenium materials
CN101899068A (en) * 2009-05-29 2010-12-01 气体产品与化学公司 Volatile group 2 metal precursors
WO2012057883A1 (en) * 2010-10-29 2012-05-03 Applied Materials, Inc. Bisamineazaallylic ligands and their use in atomic layer deposition methods

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100279067B1 (en) 1998-04-23 2001-01-15 신현국 Aluminum complex derivative for chemical vapor deposition and production of the same derivative
EP2182088B1 (en) 2002-11-15 2013-07-17 President and Fellows of Harvard College Atomic layer deposition using metal amidinates
WO2005030714A1 (en) 2003-09-25 2005-04-07 Eisai Co., Ltd. Process for the production of compounds having 5- to 10-membered aromatic heterocycles with alkylmagnesium monoamides
JP4366332B2 (en) 2004-04-02 2009-11-18 株式会社半導体エネルギー研究所 Organometallic complex, light emitting element and light emitting device using the organometallic complex
US8084145B2 (en) 2004-04-02 2011-12-27 Semiconductor Energy Laboratory Co., Ltd. Organometallic complex, light emitting element using the complex, light emitting device using the element, and electric apparatus using the device
US7619093B2 (en) 2004-10-15 2009-11-17 Praxair Technology, Inc. Organometallic compounds and mixtures thereof
US7064224B1 (en) 2005-02-04 2006-06-20 Air Products And Chemicals, Inc. Organometallic complexes and their use as precursors to deposit metal films
US7632351B2 (en) * 2005-08-08 2009-12-15 E. I. Du Pont De Nemours And Company Atomic layer deposition processes for the formation of ruthenium films, and ruthenium precursors useful in such processes
US8691668B2 (en) 2009-09-02 2014-04-08 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Dihalide germanium(II) precursors for germanium-containing film depositions
US8632853B2 (en) 2010-10-29 2014-01-21 Applied Materials, Inc. Use of nitrogen-containing ligands in atomic layer deposition methods
TWI551708B (en) 2011-07-22 2016-10-01 應用材料股份有限公司 Method of atomic layer deposition using metal precursors
US8691985B2 (en) 2011-07-22 2014-04-08 American Air Liquide, Inc. Heteroleptic pyrrolecarbaldimine precursors
US20130089678A1 (en) 2011-10-07 2013-04-11 American Air Liquide, Inc. Plasma-enhanced deposition of nickel-containing films for various applications using amidinate nickel precursors
US20130089680A1 (en) 2011-10-07 2013-04-11 American Air Liquide, Inc. Plasma-enhanced deposition of ruthenium-containing films for various applications using amidinate ruthenium precursors
US9994954B2 (en) * 2013-07-26 2018-06-12 Versum Materials Us, Llc Volatile dihydropyrazinly and dihydropyrazine metal complexes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070054487A1 (en) * 2005-09-06 2007-03-08 Applied Materials, Inc. Atomic layer deposition processes for ruthenium materials
CN101899068A (en) * 2009-05-29 2010-12-01 气体产品与化学公司 Volatile group 2 metal precursors
WO2012057883A1 (en) * 2010-10-29 2012-05-03 Applied Materials, Inc. Bisamineazaallylic ligands and their use in atomic layer deposition methods

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CN104342633A (en) 2015-02-11
KR20150013082A (en) 2015-02-04
US20180327900A1 (en) 2018-11-15
JP2015042781A (en) 2015-03-05
TW201512177A (en) 2015-04-01
US9994954B2 (en) 2018-06-12
EP2910665B1 (en) 2016-12-14
TWI552997B (en) 2016-10-11
EP2910665A1 (en) 2015-08-26
US20190292659A1 (en) 2019-09-26
JP5918316B2 (en) 2016-05-18
TW201623258A (en) 2016-07-01
TWI630200B (en) 2018-07-21
US20150030782A1 (en) 2015-01-29
US10914001B2 (en) 2021-02-09

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